Production method for hydrogel structure and intermediate of hydrogel structure

Abstract

In order to inhibit a swollen hydrogel from moving during patterning by light irradiation, a production method (M11) for a hydrogel structure includes a patterning step (S14) in which a hydrogel swollen with water is irradiated with light to perform patterning, wherein in the patterning step (S14), at least some of the side surfaces of the hydrogel are supported by a support member formed on the main surface.

Description

Method for producing hydrogel structure and intermediate for hydrogel structure

[0001] The present invention relates to a method for producing a hydrogel structure, and also to an intermediate for the hydrogel structure.

[0002] Patent Document 1 describes a technique for improving the resolution of the refractive index spatial distribution pattern by dehydrating and shrinking a swollen hydrogel that has been patterned to have a refractive index spatial distribution, compared to the resolution at the time of patterning. Patent Document 1 calls this technique Implosion Fabrication (ImpFab).

[0003] U.S. Pat. No. 1,214,661

[0004] In ImpFab, the hydrogel may be surrounded by water during the patterning process of the swollen hydrogel. This is a measure to suppress volumetric shrinkage that may occur in the hydrogel as it dehydrates. However, when the hydrogel is surrounded by water, the hydrogel tends to move on the main surface of the substrate. This movement of the hydrogel during patterning can lead to a decrease in patterning accuracy.

[0005] One aspect of the present invention has been made in view of the above-mentioned problems, and its object is to suppress the movement of a swollen hydrogel during patterning by light irradiation.

[0006] In order to solve the above problems, a method for manufacturing a hydrogel structure according to one embodiment of the present invention includes a patterning step in which a hydrogel placed on a main surface of a substrate and swollen with water is patterned by irradiating the hydrogel with light, and in the patterning step, at least a portion of the side surface of the hydrogel is supported by a support member formed on the main surface.

[0007] In order to solve the above problems, a method for manufacturing a hydrogel structure according to one embodiment of the present invention includes a patterning step in which a hydrogel covering a main surface of a substrate and swollen with water is irradiated with light to perform patterning, and a cutting step in which the hydrogel is cut into pieces of a predetermined size.

[0008] In order to solve the above problems, an intermediate of a hydrogel structure according to one embodiment of the present invention is an intermediate of a hydrogel structure comprising a substrate, a swollen hydrogel placed on the main surface of the substrate, and a sealing member that seals the substrate and the hydrogel together with water, and is configured such that at least a portion of the side of the hydrogel is supported by a support member formed on the main surface.

[0009] According to one aspect of the present invention, it is possible to suppress the movement of the swollen hydrogel during patterning by light irradiation.

[0010] FIG. 1 is a flowchart of a method for manufacturing a hydrogel structure according to a first embodiment of the present invention. FIG. 2 is a perspective view and a plan view of a substrate at the start of the method for manufacturing the hydrogel structure shown in FIG. 1. FIG. 3 is a plan view of a substrate in each step included in the method for manufacturing the hydrogel structure shown in FIG. 1. FIG. 4 is a plan view and a cross-sectional view of an intermediate of a hydrogel structure according to a second embodiment of the present invention. FIG. 5 is a schematic diagram showing a first modified example of a patterning step included in the method for manufacturing the hydrogel structure shown in FIG. 1. FIG. 6 is a schematic diagram showing a second modified example of a patterning step included in the method for manufacturing the hydrogel structure shown in FIG.

[0011] [Embodiment 1] <Method for Producing a Hydrogel Structure> A method M11 for producing a hydrogel structure according to embodiment 1 of the present invention will be described with reference to Figures 1 to 3. Note that, hereinafter, the method M11 for producing a hydrogel structure will also be simply referred to as the production method M11.

[0012] Fig. 1 is a flowchart of manufacturing method M11. Fig. 2 is a perspective view (left) and a plan view (right) of substrate 11 at the start of manufacturing method M11. Fig. 3 is a plan view of substrate 11 at each step included in manufacturing method M11.

[0013] 2, the normal direction to the main surfaces 111 and 112 of the substrate 11 is defined as the z-axis direction, and among the in-plane directions of the main surfaces 111 and 112, directions parallel to each side of the frame 12 are defined as the x-axis direction and the y-axis direction, respectively. The direction from the main surface 112 toward the main surface 111 is defined as the z-axis positive direction, and the x-axis positive direction and the y-axis positive direction are defined so as to form a left-handed Cartesian coordinate system together with the z-axis positive direction. This method of defining the Cartesian coordinate system is also common to the Cartesian coordinate system shown in FIG.

[0014] As shown in FIG. 1, the manufacturing method M11 includes a support formation step S11, a hydrogel formation step S12, a pigment dispersion step S13, a patterning step S14, a cleaning step S15, a deposition step S16, and a shrinkage step S17.

[0015] Fig. 2 shows the substrate 11 at the start of manufacturing method M11. Fig. 2 schematically shows the substrate 11 and a frame 12 formed on a main surface 111 of the substrate 11. Therefore, the dimensional ratios of the substrate 11 and the frame 12 in Fig. 2 do not necessarily match the dimensional ratios of the actual products.

[0016] As shown in Fig. 2, the substrate 11 is a plate-like member having a pair of main surfaces 111 and 112 that are parallel to each other. The shape of the substrate 11 is square when the main surface 111 is viewed in a plan view from the positive direction of the z-axis. The shape of the substrate 11 is not limited to a square, and may be a quadrangle such as a rectangle, or may be circular like a wafer. In the following, when referring to a plan view, it means the case where the main surface 111 is viewed in a plan view from the positive direction of the z-axis.

[0017] The material constituting the substrate 11 is not limited, but is preferably a material that transmits the wavelength of light used as signal light in the hydrogel structure 10 manufactured by manufacturing method M11 and in an optical composite device including the hydrogel structure 10. Examples of materials constituting the substrate 11 include glass materials such as quartz and semiconductor materials such as silicon. In this embodiment, silicon is used as the material for the substrate 11.

[0018] Furthermore, alignment marks 113 are formed at the four corners of the main surface 111. In this embodiment, the shape of the alignment marks 113 is cross-shaped, but this shape is not limited thereto. In this embodiment, the alignment marks 113 are made of a thin metal film. However, the material is not limited thereto, and may be, for example, a resin such as a photoresist.

[0019] (Support Forming Step) The support forming step S11 is a step of forming a frame body 12 on the main surface 111 (see FIG. 3). The frame body 12 is an example of a support member formed on the substrate 11. In this embodiment, the frame body 12 is annular (see FIG. 2).

[0020] The outer edge of the frame 12 has a square shape in a planar view. The width of each of the four sides of the frame 12 is uniform. Therefore, the recess 121 formed inside the frame 12 also has a square shape in a planar view. The inner wall surface of the frame 12, which defines the shape of the recess 121, is an example of a wall surface that supports at least a portion (in this embodiment, the entirety) of the side surface of the swollen hydrogel in the patterning step S14 described below. The inner wall surface of the frame 12 can also be considered to constitute a portion of the side surface of the support member. The inner and outer wall surfaces of the frame 12 are formed so as to intersect with the main surface 111 (in this embodiment, so as to be perpendicular to it). The shape of the outer edge of the frame 12 and the recess 121 in a planar view is not limited to a square, but may be a quadrangle, such as a rectangle, a polygon other than a quadrangle, or a shape without corners, such as a circle or an ellipse.

[0021] In this embodiment, hydrogel is used as the material forming the frame body 12. However, the material of the frame body 12 is not limited to this, and may be a resin, a metal, or an oxide.

[0022] Furthermore, when a hydrogel is used as the material for the frame 12, the composition of the polymer constituting the hydrogel may be the same as the composition of the polymer constituting the hydrogel structure, but it is preferably different from the composition of the polymer. That is, the hydrogel constituting the frame 12 is preferably different from the hydrogel constituting the hydrogel structure. Here, the hydrogel constituting the frame 12 preferably has a higher crosslink density than the hydrogel constituting the hydrogel structure. Crosslink density refers to the density of crosslinking points for the monomers constituting the hydrogel and is defined as "number of crosslinking points / number of monomer units." Crosslinking points refer to points where two or more main chains of the polymer constituting the hydrogel are bonded. Crosslinking points can be formed by, for example, compounds with two or more bonding sites, such as diamines, or monomers with two or more polymerization sites, such as diacrylates, but are not limited thereto. The crosslinking density of the hydrogel constituting the frame 12 is preferably at least two times, more preferably at least five times, and most preferably at least ten times, the crosslinking density of the hydrogel constituting the hydrogel structure. The upper limit of the crosslink density of the hydrogel that constitutes the frame 12 is 1000 times or less based on the crosslink density of the hydrogel that constitutes the hydrogel structure.

[0023] Furthermore, when a hydrogel is used as the material constituting the frame 12, the frame 12, which is an example of a support member, is preferably made of a water retention agent. Examples of water retention agents include acrylic polymers having at least one of acrylic acid, acrylamide, polyvinyl alcohol, and a PEG structure in their side chains, and copolymers of these acrylic polymers. Such acrylic polymers and copolymers of acrylic polymers are a form of hydrogel and are widely used as water-absorbent polymers.

[0024] In addition, in this embodiment, the frame 12 is patterned by forming a film made of hydrogel and then using photolithography, but the present invention is not limited to this.

[0025] In this embodiment, the length of each side of the square that forms the inner edge of the frame 12 is 10 mm. However, the length of each side is not limited to this and can be appropriately designed depending on the purpose of the hydrogel structure, etc. The length of each side can be, for example, 1 mm or more and 100 mm or less.

[0026] In this embodiment, the height of the frame 12 is 1 mm. However, the height is not limited to this and can be appropriately designed depending on the content of the hydrogel formation step S12 described below. The height can be 50 μm or more and 5 mm or less.

[0027] (Substrate Processing Step) Manufacturing method M11 may further include a substrate processing step (not shown in FIG. 1 ) that is performed before the hydrogel formation step S12 described below. The substrate processing step may be performed before or after the support formation step S11.

[0028] The substrate treatment step is a step of subjecting a partial region of the main surface 111 of the substrate 11 to hydrophilic treatment. By carrying out the substrate treatment step, the force generated between the partial region of the main surface 111 and the partial region of the swollen hydrogel 13 can be made greater than the force generated between the remaining region of the main surface 111 and the remaining region of the swollen hydrogel 13.

[0029] In one aspect of manufacturing method M11, a sliding treatment may be performed in addition to the substrate treatment process. The sliding treatment is a treatment that reduces the force generated between the main surface 111 and the swollen hydrogel 13 in an area of ​​the main surface 111 included in the recess 121 other than the partial area. In other words, it is a treatment that improves the sliding property at the interface between the main surface 111 and the swollen hydrogel 13. Examples of the sliding treatment include a hydrophobic treatment and a water-repellent treatment. A specific example of the water-repellent treatment is the formation of a film or coating of a fluorine-based resin.

[0030] In the substrate processing step, a photoresist film is formed as a mask on the area excluding the partial area of ​​the main surface 111. This mask can be formed appropriately using a microfabrication method such as photolithography or electron beam lithography.

[0031] Specific examples of hydrophilic treatment include acid treatment, plasma treatment, ozone treatment, etc. When these hydrophilic treatments are performed on the partial region, oxygen is exposed in a dense state in the partial region. Therefore, the partial region can bond a hydrogel (described later) to the main surface 111 by utilizing the force of hydrogen bonding.

[0032] This configuration provides the following advantages in each step after the swollen hydrogel 13 is formed inside the recess 121 in the hydrogel formation step S12 described below: That is, it is possible to reduce the possibility that the hydrogel 13 will shift position or that the swollen hydrogel 13 will jump out of the recess 121.

[0033] As a modification of the substrate treatment step, the partial region may be subjected to a chemical treatment. Here, the chemical treatment refers to a treatment in which a compound that bonds the substrate 11 with a swollen hydrogel (described later) is applied to the ends of the silicon that constitutes the surface of the partial region.

[0034] Examples of compounds used in this chemical treatment include various compounds called silane coupling agents. Preferably, the silane coupling agent contains at least one of a functional group capable of interacting with the hydrogel and a functional group capable of forming a covalent bond with the hydrogel.

[0035] Examples of silane coupling agents include chlorosilanes, alkoxysilanes, tetraethyl orthosilicate (TEOS), 3-aminopropyltriethoxysilane (APTS), and vinyltrimethoxysilane. The amino group contained in APTS can interact with the hydrogel. The methylene group contained in vinyltrimethoxysilane can form a covalent bond with the hydrogel by cleaving the double bond. Therefore, the partial region can utilize the force of bonding via the compound to bond the hydrogel (described below) to the main surface 111.

[0036] In this embodiment, the case where the hydrophilic treatment is performed on the partial region of the main surface 111 has been described. However, the partial region to be hydrophilic treated can also be set on the inner wall surface of the frame body 12 instead of the main surface 111. In this case, the partial region on the inner wall surface of the frame body 12 is bonded to a partial region of the hydrogel 13, which will be described later. Even with this configuration, it is possible to reduce the possibility that the hydrogel 13 will be displaced or that the swollen hydrogel 13 will protrude outside the recess 121.

[0037] (Hydrogel Formation Step) The hydrogel formation step S12 is a step of forming a swollen hydrogel 13 at least inside the recesses 121 of the main surface 111 (see FIG. 3 ). In the hydrogel formation step S12, the recesses 121 are filled with monomers that are raw materials for the swollen hydrogel 13, and the monomers are polymerized to obtain the swollen hydrogel 13.

[0038] In a modified example of the hydrogel formation step S12, a small piece of shrunk hydrogel that has been preformed to a predetermined shape and dimensions can be placed in the recess 121, and water can be supplied to the small piece to swell it, thereby obtaining a swollen hydrogel 13. The predetermined shape and dimensions of the shrunk hydrogel can be determined appropriately based on the shrinkage rate (or expansion rate) of the hydrogel.

[0039] The material constituting the hydrogel 13 is not limited as long as it swells upon absorbing moisture and shrinks upon releasing moisture. Examples of materials constituting the hydrogel 13 include (meth)acrylates having a carboxylic acid unit in the side chain, (meth)acrylamides having an amide group in the side chain, (meth)acrylates having an amino group in the side chain, and PEGs having a polyethylene glycol chain in the side chain or main chain (hereinafter referred to as "acrylates, etc."). Suitable materials for the hydrogel 13 include polymers and copolymers of acrylates, etc. Examples of materials constituting the hydrogel 13 include materials described in Patent Document 1 (e.g., FIG. 1A) and materials described in International Publication WO 2022 / 176376 (e.g., FIG. 2).

[0040] The hydrogel formation step S12 and the subsequent pigment dispersion step S13, washing step S15, deposition step S16, and shrinkage step S17 can be performed using the Implosion Fabrication (ImpFab) technique described in Patent Document 1. Therefore, only a brief explanation of these steps will be given.

[0041] (Pigment Dispersion Step) The pigment dispersion step S13 is a step carried out before the patterning step S14, and is a step of dispersing a pigment inside the swollen hydrogel 13.

[0042] (Patterning Step) The patterning step S14 is a step of patterning the hydrogel 13 by irradiating the swollen hydrogel 13 placed on the main surface 111 with light to bond a dye to the swollen hydrogel 13. In the patterning step S14, at least a portion of the side surface of the swollen hydrogel 13 is supported by the inner wall surface of the frame 12. In this embodiment, as shown in the plan view of the hydrogel formation step S12 in FIG. 3 , the side surface of the swollen hydrogel 13 is surrounded by the inner wall surface of the frame 12, and the entire side surface of the swollen hydrogel 13 is supported by the inner wall surface of the frame 12.

[0043] In this embodiment, the two-photon absorption method is used to bind the dye to the hydrogel 13. By performing the patterning step S14, when the main surface 111 is viewed in plan, the hydrogel 13 is formed with regions in which the content of the bound dye has a spatial distribution and regions in which the dye is not bound.

[0044] (Cleaning process) The cleaning process S15 is a process carried out after the patterning process S14, and is a process for cleaning out the pigment dispersed inside the hydrogel 13 swollen by the pigment dispersion process S13, which pigment is not bound to the swollen hydrogel 13.

[0045] (Deposition Step) The deposition step S16 is a step of further modifying the dye bonded to the inside of the swollen hydrogel 13 with functional particles or molecules. Examples of these include fine metal particles (e.g., nanoparticles), fluorescent particles, proteins, DNA, etc. In this embodiment, gold nanoparticles are modified with the dye.

[0046] The deposition step S16 may further include a step of further growing the modified particles, a step of reacting the modified molecules with an additional compound, etc. In this embodiment, the particle size of the metal particles is increased by depositing silver on the surface of the above-mentioned gold nanoparticles.

[0047] The metal particles contained in the hydrogel 13 change the refractive index of the hydrogel 13. Therefore, when signal light is incident on the hydrogel 13 and passes through the hydrogel 13, the amount of phase modulation of the signal light can be increased. This amount of phase modulation depends on the amount of metal particles contained in the hydrogel 13. Therefore, it can be said that this amount of phase modulation depends on the amount of dye contained in the hydrogel 13, and further, it can be said that it depends on the amount of light irradiated onto each region of the hydrogel 13 in the patterning step S14.

[0048] The regions patterned in the patterning step S14 (regions irradiated with light) where the dye has a spatial distribution become optically effective regions 132 where the amount of phase modulation is spatially distributed by carrying out the deposition step S16 (see the plan view of the patterning step S14 in FIG. 3). On the other hand, the regions not patterned in the patterning step S14 (regions not irradiated with light) where the dye is not bonded become optically ineffective regions 133 where the amount of phase modulation is constant. In this way, when the main surface 111 is viewed in plan, the swollen hydrogel 13 has optically effective regions 132 where the amount of phase modulation is spatially distributed and optically ineffective regions 133 where the amount of phase modulation is constant.

[0049] In addition, by appropriately selecting particles, molecules, etc. to modify the dye in the deposition step S16, it is possible to impart a spatial distribution of absorptance to the optically effective region 132. In this way, the optically effective region 132 is a region in which at least one of the absorptance and the phase modulation amount has a spatial distribution, and the optically ineffective region 133 is a region in which the absorptance and the phase modulation amount are constant.

[0050] In the plan view of the patterning step S14 and the contraction step S17 in FIG. 3, the center of gravity P Ｃ and the center of gravity P of the hydrogel 13 after contraction Ｃ and are shown as open circles. Ｃ is the intersection of two diagonals of the square hydrogel 13. In this embodiment, the contraction rate of the hydrogel 13 is set to 1 / 2. However, the contraction rate of the swollen hydrogel 13 is not limited to 1 / 2. This contraction rate can be appropriately designed depending on the selection of the material constituting the swollen hydrogel 13.

[0051] (Contraction Step) The contraction step S17 is a step of contracting the swollen hydrogel 13 (see the plan view of the contraction step S17 in FIG. 5). As described above, the contraction rate of the hydrogel 13 is 1 / 2, so the length of each side of the hydrogel 13 contracts by 1 / 2.

[0052] As described above, the hydrogel structure 10 is produced by carrying out the manufacturing method M11 (see the plan view of the shrinking step S17 in FIG. 3 ). In one aspect of the present invention, a post-treatment step, which will be described later, may be carried out after the shrinking step S17 is carried out. By carrying out the post-treatment step, an optical composite device including the hydrogel structure 10 is produced.

[0053] (Post-Processing) Manufacturing method M11 may include post-processing steps not shown in Fig. 1. The post-processing steps include a lamination step, an alignment step, and a bonding step.

[0054] In the post-treatment step, the hydrogel structure 10 manufactured by manufacturing method M11, a light source module, and a light detection module are used.

[0055] As described above, the hydrogel structure 10 is manufactured by the manufacturing method M11. In this embodiment, the center of gravity P Ｃ is the optical axis A of the hydrogel 13 in the hydrogel structure 10 １ It matches.

[0056] The light source module is a light source that irradiates signal light to be incident on the hydrogel 13 of the hydrogel structure 10. The light source module includes a substrate and a light-emitting device provided on a main surface of the substrate. The light-emitting device may be a light-emitting diode, a laser diode, or a liquid crystal panel.

[0057] In this embodiment, the shape and dimensions of the substrate of the light source module are the same as those of the substrate 11. Furthermore, alignment marks are formed at the four corners of the main surface of the substrate. The shape of the alignment marks is the same as that of the alignment marks 113. Furthermore, the position of each alignment mark on the main surface of the substrate corresponds to the position of each alignment mark 113 on the main surface 111. Therefore, when the substrate 11 and the substrate of the light source module are overlapped so that their outer edges coincide with each other in a plan view, each alignment mark 113 and each alignment mark of the light source module are perfectly aligned.

[0058] The light source module may further include an optical system provided downstream of the light emitting device, which can be used to collimate the signal light emitted by the light emitting device.

[0059] In this embodiment, the optical axis of the light-emitting device in the light source module is the optical axis A of the hydrogel 13. １ Therefore, when the outer edge of the substrate 11 and the outer edge of the substrate of the light source module are overlapped so as to coincide with each other in a plan view, the optical axis A １ and the optical axis of the light source module are perfectly aligned.

[0060] The light detection module is a photodetector that detects signal light emitted by the light emitting device of the light source module and transmitted through the hydrogel 13 of the hydrogel structure 10. The light detection module includes a substrate and a light receiving device 33 provided on the main surface of the substrate. A specific example of the light receiving device is a photodiode.

[0061] In this embodiment, the shape and dimensions of the substrate of the light detection module are the same as those of the substrate 11. Furthermore, alignment marks are formed at the four corners of the main surface of the substrate. The shapes of the alignment marks are the same as those of the alignment marks 113. Furthermore, the positions of the alignment marks on the main surface of the substrate correspond to the positions of the alignment marks 113 on the main surface 111. Therefore, when the substrate 11 and the substrate of the light detection module are overlapped so that their outer edges coincide with each other in a plan view, the alignment marks 113 and the alignment marks of the light detection module are perfectly aligned.

[0062] In this embodiment, the optical axis of the light receiving device in the light detection module is the optical axis A of the hydrogel 13. １ Therefore, when the outer edge of the substrate 11 and the outer edge of the substrate of the light detection module are overlapped so as to coincide with each other in a plan view, the optical axis A １ and the optical axis of the light detection module are perfectly aligned.

[0063] Using the hydrogel structure 10, light source module, and light detection module configured in this manner, each step of the post-processing process is carried out as follows.

[0064] The lamination step is a step of stacking the hydrogel structure 10, the light source module, and the light detection module. At this stage, the substrates have only been stacked, and therefore the alignment between the substrates has not been adjusted.

[0065] Although not shown in FIG. 2, spacers may be interposed between the substrate of the light source module and the substrate 11, and between the substrate 11 and the substrate of the light detection module to define the distance between the substrates.

[0066] The alignment process is performed on the optical axis A. １ and a process of adjusting the alignment of the substrate of the light source module, the substrate 11, and the substrate of the light detection module so that the optical axis of the light source module and the optical axis of the light detection module coincide with each other. As a method for adjusting this alignment, any existing adjustment method can be used as appropriate.

[0067] The bonding process is a process of bonding the substrate of the light source module to the substrate 11, and bonding the substrate 11 to the substrate of the light detection module, with the optical axes of the substrates aligned as described above. In this embodiment, the substrates are bonded together using a resin adhesive. However, the bonding means for bonding the substrates together is not limited to such an adhesive and can be selected as appropriate.

[0068] As described above, an optical composite device including the hydrogel structure 10 is manufactured by carrying out the manufacturing method M11 including the post-treatment step.

[0069] <Application Example of Hydrogel Structure 10> As described above, an optically effective region 132 in which at least one of the absorbance and the phase modulation amount has a spatial distribution is formed in the swollen hydrogel 13 included in the hydrogel structure 10. The optically effective region 132 configured in this manner can be made to function in the same manner as the optical diffraction element illustrated in Figure 10 of International Publication WO2022 / 176555.

[0070] Furthermore, in the patterning step S14 of manufacturing method M11, the swollen hydrogel 13 is patterned using two-photon absorption, so that a multi-stage optical diffraction element can be formed inside one hydrogel 13. Therefore, the hydrogel 13 functions not only as a single-stage optical diffraction element, but also as an optical computing device equipped with a multi-stage optical diffraction element.

[0071] The optical composite device also includes a light source module and a light detection module in addition to the hydrogel structure 10 containing the contracted hydrogel 13. Therefore, the optical composite device is an optical computing system that compactly integrates a light source that inputs signal light to the optical computing device and a photodetector that detects the signal light output from the optical computing device. In the optical composite device, the substrates in the hydrogel structure 10, the light source module, and the light detection module can be easily aligned, so that the optical axes in the optical computing system can be easily aligned.

[0072] As described above, one aspect of the present invention also includes an optical diffraction element comprising a substrate 11 and a contracted hydrogel 13 having an optically effective area 132 in which at least one of the absorbance and the phase modulation amount has a spatial distribution.

[0073] [Embodiment 2] <Intermediate of Hydrogel Structure> An intermediate 5 according to embodiment 2 of the present invention and its modified intermediate 6 will be described with reference to FIG. 4. FIG. 4 is a plan view of the intermediate 5 and the intermediate 6. FIG. 4 also shows a cross-sectional view of the intermediate 5. This cross-sectional view is obtained by viewing a cross section taken along line A-A' shown in the plan view of the intermediate 5. Both the intermediate 5 and the intermediate 6 are intermediates for producing a hydrogel structure such as the hydrogel structure 10. The Cartesian coordinate system shown in FIG. 4 is defined in the same way as the Cartesian coordinate system shown in FIG. 1.

[0074] The intermediate 5 includes a hydrogel structure 50, a sealing member 54, and water 55. The hydrogel structure 50 includes a substrate 51, a frame 52, and a swollen hydrogel 53.

[0075] The substrate 51 corresponds to the substrate 11 of the hydrogel structure 10 described in the first embodiment. However, in this embodiment, a silicon wafer is used as the substrate 51. In the hydrogel structure 10, the substrate 11 was configured so that one swollen hydrogel 13 was placed on the main surface 111 (see the plan view of the hydrogel formation step S12 in FIG. 3 ). In contrast, in the hydrogel structure 50, the substrate 51 is configured so that multiple swollen hydrogels 53 can be placed on one main surface. In the intermediate 5 thus produced, at least a portion (all of the side surface in this modification) of the hydrogel 53 is supported by the inner surface (one aspect of the wall surface) of the frame 52.

[0076] Furthermore, four alignment marks 513 are formed on the main surface of the substrate 51. The alignment marks 513 correspond to the alignment marks 113 formed on the main surface 111 of the substrate 11.

[0077] A frame 52 is formed on the main surface of the substrate 51 so as to avoid the area where the four alignment marks 513 are formed. The frame 52 is made of hydrogel, like the frame 12. However, unlike the frame 12, the frame 52 is required to define the positions of multiple swollen hydrogels 53. Therefore, as shown in the plan view of the intermediate 5 in FIG. 4 , the frame 52 has 48 recesses formed in a grid pattern so that 48 swollen hydrogels 53 can be placed thereon. Therefore, unlike the ring-shaped frame 12, the shape of the frame 52 is a lattice pattern. These 48 recesses all have the same shape and dimensions and are formed periodically in both the x-axis direction and the y-axis direction.

[0078] A swollen hydrogel 53 similar to the swollen hydrogel 13 is placed in each recess. That is, the hydrogel structure 50 includes 48 swollen hydrogels 53. As described above, the 48 recesses of the frame 52 are formed periodically, and therefore the centers of gravity of the 48 swollen hydrogels 53 contained in those recesses are also arranged periodically.

[0079] The sealing member 54 seals the substrate 51 and the plurality of swollen hydrogels 53 together with water 55. In this embodiment, the sealing member 54 is composed of two resin sheets. Each sheet is rectangular in plan view and formed into a bag shape by fusing the area along its outer edge. By sealing the hydrogel structure 50 with the sealing member 54 in this manner, the hydrogel structure 50 can be stored without the swollen hydrogels 53 shrinking due to dehydration.

[0080] 4, as long as it is possible to seal the hydrogel structure 50 and the sealing member 54. The sealing member 54 may be shaped like a wafer tray that accommodates wafers one by one, or like a wafer case that accommodates multiple wafers together.

[0081] <Modification of Intermediate Body of Hydrogel Structure> In the hydrogel structure 50 described above, a frame 52 was used to define the positions of the multiple swollen hydrogels 53. However, in intermediate body 6, which is a modification of intermediate body 5, the swollen hydrogel is formed so as to cover the main surface of the substrate, making it possible to omit the frame 52. In this modification, a configuration in which the frame 52 is omitted will be described.

[0082] The intermediate 6 includes a hydrogel structure 60, a sealing member 64, and water 65. The sealing member 64 and the water 65 correspond to the sealing member 54 and the water 55, respectively, and therefore will not be described here.

[0083] The hydrogel structure 60 includes a substrate 61 and a swollen hydrogel 63. The substrate 61 and the alignment marks 613 formed on the main surface of the substrate 61 correspond to the substrate 51 and the alignment marks 513 formed on the main surface of the substrate 51, respectively, and therefore, a description thereof will be omitted here.

[0084] In the hydrogel structure 60, no frame is formed on the main surface of the substrate 61. Therefore, in the hydrogel formation step S12, a solid film of swollen hydrogel is formed over the entire main surface of the substrate 61. In other words, the swollen hydrogel covers the main surface of the substrate 61.

[0085] In addition, in manufacturing method M11 for producing the hydrogel structure 60, after the hydrogel formation step S12, a cutting step is performed in which the solid swollen hydrogel is cut into swollen hydrogels 63 having a predetermined shape and size. As shown in the plan view of the intermediate 6 in FIG. 4 , a plurality of swollen hydrogels 63 are obtained by cutting lattice-shaped cut lines 62 into the solid swollen hydrogel. The number of swollen hydrogels 63 in the hydrogel structure 60 is 48, the same as the number of swollen hydrogels 53 in the hydrogel structure 50. In the intermediate 6 produced in this manner, at least a portion (all in this modification) of the side surfaces of the hydrogels 63 are supported by the side surfaces (one aspect of the wall surface) of the adjacent swollen hydrogels 63.

[0086] The manufacturing method M11 for manufacturing the hydrogel structure 60 includes a patterning step S14 and a cutting step, similar to the manufacturing method M11 shown in Fig. 1. In this manufacturing method M11, it does not matter which step, the patterning step S14 or the cutting step, is performed first.

[0087] [Modification of Patterning Step] Below, a first modification and a second modification of the patterning step S14 included in the method M11 for manufacturing a hydrogel structure shown in FIG. 1 will be described with reference to FIGS. 5 and 6, respectively. FIGS. 5 and 6 are schematic diagrams showing the first modification and the second modification of the patterning step S14, respectively. More specifically, FIG. 5 is a plan view and a cross-sectional view of a hydrogel structure 70 patterned in the first modification, and FIG. 6 is a cross-sectional view of a hydrogel structure 70 patterned in the second modification. Note that in the cross-sectional views of FIGS. 5 and 6, the z-axis direction is exaggerated to make the structure in the z-axis direction easier to understand. The Cartesian coordinate systems shown in FIGS. 5 and 6 are defined in the same way as the Cartesian coordinate system shown in FIG. 1.

[0088] <First Modification> In the first modification, the medium to be patterned is a hydrogel structure 70 (see FIG. 5 ). The hydrogel structure 70 includes a substrate 71, an alignment mark 713, a frame 72, multiple swollen hydrogels 73, and a dam 74. The hydrogel structure 70 is a modification of the hydrogel structure 50 shown in FIG. 4 . That is, (1) the substrate 71, (2) the alignment mark 713, (3) the frame 72, and (4) the swollen hydrogels 73 in the hydrogel structure 70 correspond to (1) the substrate 51, (2) the alignment mark 513, (3) the frame 52, and (4) the swollen hydrogels 53 in the hydrogel structure 50, respectively. Therefore, descriptions of the substrate 71, the alignment mark 713, the frame 72, and the swollen hydrogels 73 will be omitted here.

[0089] 5, a configuration is adopted in which the height of the swollen hydrogel 73 (the length from the main surface 711 of the substrate 71 to the upper end of the swollen hydrogel 73) exceeds the height of the frame body 72 (the length from the main surface 711 to the upper end of the frame body 72). However, the relationship in size between the height of the swollen hydrogel 73 and the height of the frame body 72 is not limited to this and can be determined as appropriate.

[0090] Weir 74 is a wall-like member formed to surround frame 72 (including the inner wall surface surrounding swollen hydrogel 73) when the main surface 711 of substrate 71 is viewed from above. As shown in the plan view of Fig. 5, weir 74 is formed in a ring shape along the outer edge of substrate 71. Furthermore, as shown in the cross-sectional view of Fig. 5, weir 74 is formed to intersect with main surface 711, and its bottom surface is in close contact with main surface 711 without any gaps.

[0091] In this modification, as shown in the cross-sectional view of FIG. 5 , the height of the weir 74 (the length from the main surface 711 to the top end of the weir 74) is preferably greater than the height of the frame 72. With this configuration, water is poured into an inner region 741 surrounded by the weir 74 (i.e., the inside of the frame 72), whereby the water is stored in the inner region 741. Furthermore, since the water level stored in the inner region 741 exceeds the height of the frame 72, the water can be supplied to the swollen hydrogel 73 via the frame 72. Here, the water level refers to the depth of the water stored in the inner region 741 in a region where surface tension is not acting (i.e., a region where the surface is horizontal). When the substrate 71 is placed so that the main surface 711 is horizontal in the patterning step S14, the water level can be considered uniform.

[0092] Furthermore, it is more preferable that the height of the weir 74 be higher than the height of each of the frame 72 and the swollen hydrogel 73. With this configuration, when water is poured into the inner region 741, the water level exceeds the height of the frame 72 and the swollen hydrogel 73, allowing water to be directly supplied to the swollen hydrogel 73. Furthermore, since the water level exceeds the height of the frame 72 and the swollen hydrogel 73, a water immersion lens can be used as the objective lens 81 (see the cross-sectional view of FIG. 5 ). Furthermore, since a large amount of water can be stored in the inner region 741, it is possible to prevent the swollen hydrogel 73 from shrinking due to dehydration over a long period of time, even without using the water supply device 82 (described later).

[0093] The material constituting the weir 74 may be a material that allows water to permeate when water is poured into the inner region 741, but is preferably a material that can store water for a predetermined period of time. Furthermore, this material is more preferably a material that does not allow water to permeate. This configuration can prevent the water stored in the inner region 741 from leaking out of the weir 74.

[0094] In this embodiment, resin is used as the material forming the dam 74. However, the material of the dam 74 is not limited to this, and may be metal or oxide (for example, glass).

[0095] 5, in a first modified example of the patterning step S14, water is stored in an inner region 741 of the weir 74. Here, the exposure apparatus used in the patterning step S14 includes an objective lens 81 and a water supply device 82.

[0096] The objective lens 81 constitutes part of the optical system of an exposure apparatus that irradiates the swollen hydrogel 73 with light to pattern the swollen hydrogel 73. In this modification, a water immersion lens is used as the objective lens 81. When using a water immersion lens as the objective lens 81 in this manner, it is preferable that the height of the weir 74 exceeds the working distance of the objective lens 81. With this configuration, when interposing water between the swollen hydrogel 73 and the exit surface of the objective lens 81, it is not necessary to rely on the surface tension of the water, and the exit surface of the objective lens 81 can be reliably immersed in water.

[0097] However, when the patterning step S14 is performed in a state in which the water level in the inner region 741 is lower than the height of the swollen hydrogel 73 and the upper end of the swollen hydrogel 73 is exposed to air, a lens used with its exit surface in contact with air (a so-called dry lens) can also be used as the objective lens 81. Note that even when the water level in the inner region 741 is lower than the height of the swollen hydrogel 73, a water immersion lens can also be used as the objective lens 81. That is, as will be described later as one aspect of a first modified example, water is interposed between the exit surface of the objective lens 81 and the swollen hydrogel 73 that is irradiated with light.

[0098] The water supply device 82 is an example of a means for steadily or intermittently supplying water to the swollen hydrogel 73 placed in the inner region 741. Accordingly, in this modification, water is steadily or intermittently supplied to the swollen hydrogel 73. In this modification, a dropper is used as an example of the water supply device 82 (see the cross-sectional view of FIG. 5 ). However, the water supply device 82 is not limited to a dropper and may be a syringe or a pump. Furthermore, the water supply device 82 may be a manual device in which the amount of water supplied is controlled by an operator, or may be an automatic device controlled by a computer.

[0099] Furthermore, it is preferable that water supply device 82 is configured to supply an amount of water close to the amount of water evaporation per unit time in inner region 741. It is more preferable that water supply device 82 is configured to supply an amount of water equal to the amount of water evaporation per unit time. Examples of water supply devices that can continuously supply a small amount of water per unit time include a microsyringe pump, a microfeeder, a dosing pump, and a tube pump.

[0100] As described above, in the first modified example, a configuration is adopted in which water is supplied from a water supply device 82 so that water continues to be present between the exit surface of the objective lens 81 used for light irradiation and the swollen hydrogel 73 that is irradiated with light.

[0101] In the first modified example, the height of the weir 74 is configured to be greater than the height of the frame 72 and greater than the working distance of the objective lens 81. With this configuration, water can be interposed between the exit surface of the objective lens 81, which is a water immersion lens, and the swollen hydrogel 73 on which patterning (i.e., light is irradiated) without substantially utilizing the surface tension of water. However, in one aspect of the first modified example, water can also be interposed between the exit surface and the swollen hydrogel 73 on which patterning is performed by utilizing the surface tension of water. In this case, the height of the weir 74 may be less than the working distance, may be less than the height of the frame 72, or may even be omitted.

[0102] As described above, when utilizing the surface tension of water in the patterning step S14, it is preferable that the water supply device 82 supplies water so that water remains between the exit surface of the objective lens 81 and the swollen hydrogel 73 irradiated with light. To achieve this, it is preferable that the water supply device 82 supply water near the objective lens 81 or on a side of the objective lens 81, or that the timing and amount of water supplied by the water supply device 82 be appropriately set. When the water supply device 82 supplies water to the side of the objective lens 81, the supplied water flows down the side of the objective lens 81 and reaches between the exit surface of the objective lens 81 and the swollen hydrogel 73 irradiated with light. According to one aspect of the first modified example, it is possible to prevent the water present between the exit surface and the swollen hydrogel 73 from drying up. Therefore, even when the patterning step S14 is performed over a long period of time, the objective lens 81 can be appropriately used as a water immersion lens.

[0103] As described above, in the first modified example and one aspect thereof, the water present between the light exit surface and the irradiated swollen hydrogel 73 may or may not utilize surface tension. In other words, the water level may be located above or below the light exit surface. Furthermore, the water present between the light exit surface and the irradiated swollen hydrogel 73 may be (1) a puddle-like state (as shown in FIG. 5 ) that uniformly covers the entire principal surface, or (2) a droplet-like state (not shown) that covers only a portion of the principal surface in a region including the swollen hydrogel 73 that is irradiated with light in the patterning step S14. In the former case, the depth of the water from the principal surface is uniform. On the other hand, in the latter case, the depth of the water from the principal surface (i.e., the thickness of the water droplet from the principal surface) is not uniform but has a distribution according to surface tension. In the latter case, it is preferable that the water covers the surface of the frame 72. By covering the surface of the frame body 72 with water, dehydration can be reliably reduced not only in the swollen hydrogel 73 that has been irradiated with light in the patterning process S14, but also in the swollen hydrogel 73 that has not been irradiated with light.

[0104] <Second Modification> In the second modification, the medium to be patterned is the hydrogel structure 70, as in the first modification (see FIG. 6). Therefore, a description of the hydrogel structure 70 will be omitted here.

[0105] The exposure apparatus used in this modification example includes a chamber 83 and a humidifier 84 in addition to the configuration of the exposure apparatus used in the first modification example (see FIG. 6).

[0106] The chamber 83 is an example of a box that separates an internal space 831 from an external space 832, which is a space other than the internal space 831. The chamber 83 accommodates at least an objective lens 81 of the optical system of the exposure apparatus and a medium to be patterned (the hydrogel structure 70 in this modification) in the internal space 831. The chamber 83 prevents water vapor introduced from a humidifier 84 (described later) from leaking, and maintains the relative humidity H ＩIn order to maintain a high level of humidity, it is preferable that the box has airtightness. An example of such a box other than the chamber is a glove box.

[0107] The humidifier 84 increases the relative humidity of the atmosphere by emitting water vapor. The method by which the humidifier 84 emits water vapor is not limited. In this modified example, the humidifier 84 is placed in the external space 832 of the chamber 83, and the water vapor emitted from the humidifier 84 is introduced into the internal space 831. However, the humidifier 84 may also be placed in the internal space 831 and configured to emit water vapor directly into the internal space 831.

[0108] As described above, the chamber 83 is airtight, and water vapor is introduced into the internal space 831. Therefore, in this modification, the relative humidity H Ｉ is the relative humidity H of the external space 832 Ｏ This configuration can reduce the amount of evaporation per unit time of the water 75 stored in the weir 74 during the patterning process. Ｉ is preferably 90% RH or higher, and more preferably 100% RH.

[0109] In this modification, the amount of evaporation per unit time can be reduced, so the water supply device 82 shown in FIG. 5 can be omitted. Furthermore, in this modification, a large amount of water vapor exists in the internal space 831, and this water vapor can be used to maintain the hydrogel 73 in a swollen state. Therefore, in this modification, the weir 74 provided on the main surface 711 of the substrate 71 can also be omitted. Even in this case, a water immersion lens can be used as the objective lens 81 by utilizing the surface tension of water to place water droplets between the swollen hydrogel 73 and the exit surface of the objective lens 81.

[0110] Furthermore, as described in the first modified example, when the patterning process S14 is performed with the upper end of the swollen hydrogel 73 exposed to the air, it is preferable to use a lens (a so-called dry lens) that is used with its exit surface in contact with the air as the objective lens 81.

[0111] [Summary] The method for manufacturing a hydrogel structure according to the first aspect of the present invention includes a patterning step in which a hydrogel placed on a main surface of a substrate and swollen with water is patterned by irradiating the hydrogel with light, and in the patterning step, at least a portion of the side surface of the hydrogel is supported by a support member formed on the main surface.

[0112] According to the above configuration, since at least a portion of the side surface of the hydrogel is supported by the support member, the degree of freedom of movement of the hydrogel in the in-plane direction of the main surface is limited, and therefore, the present manufacturing method can suppress movement of the swollen hydrogel during patterning by light irradiation.

[0113] In the method for producing a hydrogel structure according to the second aspect of the present invention, in addition to the configuration of the method for producing a hydrogel structure according to the first aspect described above, a configuration is adopted in which, in the patterning step, the swollen hydrogel is supported by the wall surfaces of the support member, and the wall surfaces are formed so as to intersect with the main surface.

[0114] According to the above configuration, it is possible to reliably suppress the movement of the swollen hydrogel during patterning by light irradiation.

[0115] In the method for manufacturing a hydrogel structure according to the third aspect of the present invention, in addition to the configuration of the method for manufacturing a hydrogel structure according to the first or second aspect described above, a configuration is adopted in which, in the patterning step, the side surface is surrounded by the support member.

[0116] According to the above configuration, the movement of the swollen hydrogel during patterning by light irradiation can be suppressed in all directions.

[0117] In the method for producing a hydrogel structure according to the fourth aspect of the present invention, in addition to the configuration of the method for producing a hydrogel structure according to the third aspect described above, a configuration is adopted in which, in the patterning step, all of the side surfaces are supported by the support members.

[0118] According to the above configuration, the movement of the swollen hydrogel during patterning by light irradiation can be reliably suppressed in all directions.

[0119] In the method for producing a hydrogel structure according to the fifth aspect of the present invention, in addition to the configuration of the method for producing a hydrogel structure according to any one of the first to fourth aspects described above, the support member is made of a water retention agent.

[0120] According to the above configuration, moisture can be supplied to the hydrogel from the support member made of a water retention agent in the patterning step, and therefore, the present manufacturing method can suppress shrinkage of the swollen hydrogel.

[0121] In the method for producing a hydrogel structure according to the sixth aspect of the present invention, in addition to the configuration of the method for producing a hydrogel structure according to the fifth aspect described above, the water retention agent is a hydrogel different from the swollen hydrogel and has a higher crosslink density than the swollen hydrogel.

[0122] According to the above configuration, the hydrogel constituting the support member has a higher crosslink density than the swollen hydrogel, so the support member can firmly support the swollen hydrogel.

[0123] The method for producing a hydrogel structure according to the seventh aspect of the present invention employs, in addition to the configuration of the method for producing a hydrogel structure according to any one of the first to sixth aspects described above, a configuration in which water is supplied to the swollen hydrogel steadily or intermittently in the patterning step.

[0124] According to the above configuration, the contraction of the swollen hydrogel can be suppressed for a long period of time, and therefore, even when performing complex patterning that requires a long period of time, the contraction of the swollen hydrogel can be suppressed.

[0125] In the method for producing a hydrogel structure according to the eighth aspect of the present invention, in addition to the configuration of the method for producing a hydrogel structure according to any one of the first to seventh aspects described above, the following configuration is adopted in the patterning step: (1) the substrate, the swollen hydrogel, and the support member are contained in the internal space of a box, and (2) the relative humidity of the internal space is higher than the relative humidity of the external space, which is a space other than the internal space.

[0126] According to the above configuration, it is possible to suppress contraction of the swollen hydrogel.

[0127] In the method for manufacturing a hydrogel structure according to the ninth aspect of the present invention, in addition to the configuration of the method for manufacturing a hydrogel structure according to any one of the first to eighth aspects described above, a configuration is adopted in which, when the main surface is viewed in a plane, a dam is formed that surrounds the support member and has a height from the main surface that is higher than that of the support member, and water is stored inside the dam during the patterning process.

[0128] According to the above configuration, the contraction of the swollen hydrogel can be suppressed for a long period of time, and therefore, even when performing complex patterning that requires a long period of time, the contraction of the swollen hydrogel can be suppressed.

[0129] In the method for manufacturing a hydrogel structure according to the tenth aspect of the present invention, in addition to the configuration of the method for manufacturing a hydrogel structure according to the ninth aspect described above, a configuration is adopted in which the height of the weir exceeds the working distance of the objective lens used for light irradiation in the patterning process, and in the patterning process, the exit surface of the objective lens is immersed in water stored inside the weir.

[0130] According to the above configuration, a water immersion lens can be used as the objective lens used for light irradiation in the patterning step.

[0131] In the method for producing a hydrogel structure according to the eleventh aspect of the present invention, in addition to the configuration of the method for producing a hydrogel structure according to any one of the first to tenth aspects described above, a configuration is adopted in which water is supplied in the patterning step so that water is continuously present between the exit surface of the objective lens used for light irradiation and the swollen hydrogel that is irradiated with light.

[0132] According to the above configuration, the amount of water present between the exit surface and the swollen hydrogel to be irradiated with light (i.e., the swollen hydrogel to be patterned) is reduced through the patterning process, thereby preventing the exit surface from being exposed.

[0133] The method for producing a hydrogel structure according to a twelfth aspect of the present invention employs a configuration including a patterning step of covering a main surface of a substrate with a hydrogel swollen with water and irradiating the hydrogel with light to perform patterning, and a cutting step of cutting the hydrogel into pieces of a predetermined size.

[0134] According to the above configuration, the hydrogel swollen with water covers the main surface. Therefore, the swollen hydrogel is less likely to move in the in-plane direction of the main surface than when the swollen hydrogel is formed only on a portion of the main surface. In this manufacturing method, it does not matter which step, the patterning step or the cutting step, is performed first. Even if the cutting step is performed before the patterning step, the side surfaces of the cut hydrogels are in contact with each other, so the degree of freedom of movement in the in-plane direction of the main surface is limited compared to when the swollen hydrogel is formed only on a portion of the main surface.

[0135] Furthermore, a method for producing a hydrogel structure according to a thirteenth aspect of the present invention, in addition to the configuration of the method for producing a hydrogel structure according to any one of the first to twelfth aspects described above, further includes a pigment dispersion step carried out before the patterning step and a washing step carried out after the patterning step, in which the pigment dispersion step is a step of dispersing a pigment inside the swollen hydrogel, the patterning step is a step of irradiating the swollen hydrogel with light to bond the pigment to the swollen hydrogel, and the washing step is a step of washing off the pigment that has been dispersed inside the hydrogel by the pigment dispersion step and that has not bonded to the swollen hydrogel.

[0136] The method for producing a hydrogel structure according to one aspect of the present invention can be suitably applied to ImpFab.

[0137] The intermediate of the hydrogel structure according to the fourteenth aspect of the present invention is an intermediate of the hydrogel structure comprising a substrate, a swollen hydrogel placed on the main surface of the substrate, and a sealing member that seals the substrate and the hydrogel together with water, and is configured such that at least a portion of the side of the hydrogel is supported by a support member formed on the main surface.

[0138] The intermediate for the hydrogel structure according to one aspect of the present invention has the same effects as the method for producing the hydrogel structure according to one aspect of the present invention.

[0139] [Summary 2] The method for manufacturing a hydrogel structure according to the first aspect of the present invention comprises: patterning a hydrogel placed on a main surface of a substrate and swollen with water by irradiating the hydrogel with light; and supporting the side surfaces of the hydrogel by a frame formed on the main surface of the substrate when patterning the hydrogel.

[0140] A method for manufacturing a hydrogel structure according to a second aspect of the present invention is the method for manufacturing a hydrogel structure according to the first aspect, wherein supporting the side surface of the hydrogel includes supporting the hydrogel by a wall surface of the frame formed so as to intersect with the main surface of the substrate.

[0141] A method for manufacturing a hydrogel structure according to a third aspect of the present invention is the method for manufacturing a hydrogel structure according to the first aspect, wherein supporting the side surfaces of the hydrogel includes surrounding the side surfaces of the hydrogel with the frame body.

[0142] A fourth aspect of the present invention relates to a method for manufacturing a hydrogel structure, which is the method for manufacturing a hydrogel structure according to the third aspect, and in which supporting the side surfaces of the hydrogel includes supporting the entire side surfaces of the hydrogel with the frame body.

[0143] A method for producing a hydrogel structure according to a fifth aspect of the present invention is the method for producing a hydrogel structure according to the first aspect, wherein the frame is made of a water retention agent.

[0144] A sixth aspect of the present invention relates to a method for producing a hydrogel structure, which is the method for producing a hydrogel structure according to the fifth aspect, wherein the water retention agent is a hydrogel different from the swollen hydrogel and has a higher crosslink density than the swollen hydrogel.

[0145] A method for producing a hydrogel structure according to a seventh aspect of the present invention is the method for producing a hydrogel structure according to the first aspect, further comprising constantly or intermittently supplying water to the hydrogel when patterning the hydrogel.

[0146] The method for manufacturing a hydrogel structure according to an eighth aspect of the present invention is the method for manufacturing a hydrogel structure according to the first aspect, further comprising the steps of: when patterning the hydrogel, accommodating the substrate, the hydrogel, and the frame in the internal space of a box; and setting the relative humidity of the internal space higher than the relative humidity of an external space, which is a space other than the internal space.

[0147] A method for manufacturing a hydrogel structure according to a ninth aspect of the present invention is the method for manufacturing a hydrogel structure according to the first aspect, further comprising forming a dam that surrounds the frame body when the main surface of the substrate is viewed in a plane and has a height from the main surface of the substrate that is higher than that of the frame body, and storing water inside the dam when patterning the hydrogel.

[0148] A tenth aspect of the present invention relates to a method for manufacturing a hydrogel structure according to the ninth aspect, wherein the height of the weir exceeds the working distance of an objective lens used when irradiating light onto the hydrogel, and when patterning the hydrogel, the exit surface of the objective lens is immersed in water stored inside the weir.

[0149] The method for manufacturing a hydrogel structure according to an eleventh aspect of the present invention is the method for manufacturing a hydrogel structure according to the first aspect, further comprising the step of supplying water so that water remains interposed between the hydrogel and the exit surface of an objective lens used to irradiate the hydrogel with light when patterning the hydrogel.

[0150] A method for producing a hydrogel structure according to a twelfth aspect of the present invention includes patterning the hydrogel by covering a main surface of a substrate and irradiating light onto the hydrogel swollen with water, and cutting the hydrogel into pieces of a predetermined size.

[0151] A method for manufacturing a hydrogel structure according to a thirteenth aspect of the present invention is the method for manufacturing a hydrogel structure according to the first aspect, further comprising dispersing a dye inside the hydrogel before patterning the hydrogel, wherein patterning the hydrogel includes irradiating the hydrogel with light to bond the dye to the hydrogel, and further comprising washing away, after patterning the hydrogel, the dye dispersed inside the hydrogel that is not bonded to the hydrogel.

[0152] A method for manufacturing a hydrogel structure according to a fourteenth aspect of the present invention is the method for manufacturing a hydrogel structure according to the twelfth aspect, further comprising dispersing a dye inside the hydrogel before patterning the hydrogel, wherein patterning the hydrogel includes irradiating the hydrogel with light to bond the dye to the hydrogel, and further comprising washing away, after patterning the hydrogel, the dye dispersed inside the hydrogel that is not bonded to the hydrogel.

[0153] The intermediate of the hydrogel structure according to the fifteenth aspect of the present invention comprises a substrate, a swollen hydrogel placed on the main surface of the substrate, and a sealing member that seals the substrate and the hydrogel together with water, and the side of the hydrogel is supported by a frame on the main surface of the substrate.

[0154] [Additional Notes] The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.

[0155] REFERENCE SIGNS LIST 10 Hydrogel structure 11 Substrate 111, 112 Main surface 113 Alignment mark 12 Frame 13 Hydrogel

Claims

1. A method for producing a hydrogel structure, comprising: a patterning step of irradiating light to a hydrogel placed on a principal surface of a substrate and swollen with water to perform patterning; and in the patterning step, at least a portion of a side surface of the hydrogel is supported by a support member formed on the principal surface.

2. The method for producing a hydrogel structure as described in claim 1, characterized in that, in the patterning process, the swollen hydrogel is supported by a wall surface of the support member, and the wall surface is formed so as to intersect with the main surface.

3. The method for producing a hydrogel structure according to claim 1 or 2, characterized in that in the patterning step, the side surface is surrounded by the support member.

4. The method for producing a hydrogel structure according to claim 3, characterized in that in the patterning step, the entire side surface is supported by the support member.

5. The method for producing a hydrogel structure according to any one of claims 1 to 4, characterized in that the support member is made of a water retention agent.

6. The method for producing a hydrogel structure according to claim 5, characterized in that the water retention agent is a hydrogel different from the swollen hydrogel and has a higher crosslink density than the swollen hydrogel.

7. The method for producing a hydrogel structure according to any one of claims 1 to 6, characterized in that, in the patterning step, water is supplied to the swollen hydrogel steadily or intermittently.

8. A method for producing a hydrogel structure described in any one of claims 1 to 7, characterized in that in the patterning process, (1) the substrate, the swollen hydrogel, and the support member are contained in the internal space of a box, and (2) the relative humidity of the internal space is higher than the relative humidity of an external space, which is a space other than the internal space.

9. A method for producing a hydrogel structure described in any one of claims 1 to 8, characterized in that, when the main surface is viewed in a plane, a dam is formed which surrounds the support member and has a height from the main surface that is higher than that of the support member, and water is stored inside the dam during the patterning process.

10. A method for producing a hydrogel structure as described in claim 9, characterized in that the height of the dam exceeds a working distance of an objective lens used for light irradiation in the patterning process, and in the patterning process, the exit surface of the objective lens is immersed in water stored inside the dam.

11. A method for producing a hydrogel structure according to any one of claims 1 to 10, characterized in that in the patterning process, water is supplied so that water is continuously present between the exit surface of an objective lens used for light irradiation and the swollen hydrogel irradiated with light.

12. A method for producing a hydrogel structure, comprising: a patterning step of covering a main surface of a substrate and patterning the hydrogel by irradiating the hydrogel with light after the hydrogel has been swollen with water; and a cutting step of cutting the hydrogel into pieces of a predetermined size.

13. A method for producing a hydrogel structure according to any one of claims 1 to 12, further comprising a pigment dispersion step carried out before the patterning step, and a washing step carried out after the patterning step, wherein the pigment dispersion step is a step of dispersing a pigment inside the swollen hydrogel, the patterning step is a step of bonding the pigment to the swollen hydrogel by irradiating the swollen hydrogel with the light, and the washing step is a step of washing the pigment that has been dispersed inside by the pigment dispersion step and that has not bonded to the swollen hydrogel.

14. An intermediate hydrogel structure comprising a substrate, a swollen hydrogel placed on a main surface of the substrate, and a sealing member that seals the substrate and the hydrogel together with water, wherein at least a portion of a side surface of the hydrogel is supported by a support member formed on the main surface.

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